CN1699444A - Polishing compositions for controlling metal interconnect removal rate in semiconductor wafers - Google Patents

Polishing compositions for controlling metal interconnect removal rate in semiconductor wafers Download PDF

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Publication number
CN1699444A
CN1699444A CNA2005100788129A CN200510078812A CN1699444A CN 1699444 A CN1699444 A CN 1699444A CN A2005100788129 A CNA2005100788129 A CN A2005100788129A CN 200510078812 A CN200510078812 A CN 200510078812A CN 1699444 A CN1699444 A CN 1699444A
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poly
thermoplastic polymer
polishing
composition
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R·L·小拉维
J·匡西
叶倩萩
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K93/00—Floats for angling, with or without signalling devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/7684—Smoothing; Planarisation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K91/00—Lines
    • A01K91/03—Connecting devices

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Environmental Sciences (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Animal Husbandry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

A polishing composition suitable for polishing semiconductor substrates comprises 0.001 to 2 wt % of a thermoplastic polymer; and 0.001 to 1 wt % of polyvinylpyrrolidone; wherein varying the weight ratio of thermoplastic polymer to the polyvinylpyrrolidone controls the removal rate of the non-ferrous interconnect.

Description

Be used for controlling the polishing composition of the metal interconnected removal speed of semiconductor wafer
Technical field
The disclosure relates to the polishing of semiconductor wafer and more specifically, relates to polishing composition and method with the metal interconnected removal speed in the control semiconductor wafer.
Background technology
Semi-conductor industry adopts interconnecting metal to form unicircuit on semiconductor wafer.These interconnecting metals are preferably non-ferrous metal.The alloy that the suitable example of this non-iron interconnecting metal has aluminium, copper, gold, nickel and platinum metals, silver, tungsten and comprises at least a above-mentioned metal.These interconnecting metals have low resistivity.Copper is metal interconnected to provide good specific conductivity with low cost.Because copper is easily molten in many dielectric substances, the silicon-dioxide of silicon-dioxide and doping type for example, unicircuit manufacturers typically adopts diffusion impervious layer to be diffused into dielectric layer to prevent copper.For example, be used to protect dielectric blocking layer to comprise tantalum, tantalum nitride, tantalum-silicon nitride, titanium, titanium nitride, titanium-silicon nitride, titanium-titanium nitride, titanium-tungsten, tungsten, tungsten nitride and tungsten-silicon nitride.
In the manufacturing of semiconductor wafer, after the metal interconnecting layer deposition, utilize polishing composition to come the polishing semiconductor substrate.Typically, this glossing adopts specially designed " the first step " slurry to remove metal interconnected fast.After this glossing comprises " second step " slurry that is used to remove the blocking layer.The second step slurry is optionally removed the blocking layer and the physical structure or the electrical property of interconnection structure is not had disadvantageous effect.
The patent US6443812 of Costas etc. discloses a kind of polishing composition that includes organic polymer, this organic polymer has the main chain that comprises at least 16 carbon atoms, and wherein this polymkeric substance has the part that surface group on a plurality of and the semiconductor wafer surface has avidity.But, the depression of this polishing composition can not prevent low-k dielectric layer and can not realize the control of the removal speed of low-k dielectric substance.Said composition can not realize the adjustment of slurry in addition.
Still there is unsatisfied demand to being used to control non-iron interconnecting metal removal speed with the water-based polished composition of controlling low-k and ultralow-k dielectric substance removal speed.
Summary of the invention
Disclosed herein is a kind of polishing composition that is applicable to the polishing semiconductor substrate, said composition comprises the thermoplastic polymer of 0.001-2wt%; Polyvinylpyrrolidone with 0.001-1wt%; Wherein the weight of polyvinylpyrrolidone is recently controlled the removal speed of nonferrous metal interconnects by increasing thermoplastic polymer.
Here also disclose a kind of polishing composition that is applicable to the polishing semiconductor substrate, said composition comprises that the weight-average molecular weight of 0.001-2wt% is the polyvinyl alcohol of 13000-23000g/ mole; The weight-average molecular weight of 0.001-1wt% is the polyvinylpyrrolidone of 3000-10000g/ mole; The coordination agent of the highest 15wt%; The corrosion inhibitor of the highest 10wt%; The oxygenant of the highest 10wt%; Silica abrasive with 0.1-40wt%; Wherein the pH value of this polishing composition is at least 7, and wherein increases the removal speed of thermoplastic polymer to the weight ratio control nonferrous metal interconnects of polyvinylpyrrolidone.
Here also disclose a kind of method of polishing semiconductor substrate, this method comprises the steps: and will comprise the thermoplastic polymer of 0.001-2wt%; Be applied to the semiconductor-based end with the polishing composition of the polyvinylpyrrolidone of 0.001-1wt%; And be equal to or less than this semiconductor wafer of polishing under 21.7 kPas the pad pressure condition, wherein increase the removal speed of thermoplastic polymer to the weight ratio control nonferrous metal interconnects of polyvinylpyrrolidone.
Embodiment
The thermoplastic polymer that can use in polishing composition has oligopolymer, polymkeric substance, ionomer, branch-shape polymer, multipolymer such as segmented copolymer, graft copolymer, star block copolymer, random copolymers etc. perhaps comprise the combination of at least a above-mentioned polymkeric substance.The suitable example that can be used for the thermoplastic polymer of polishing composition has polyacetals, and polyacrylic is polycarbonate-based, polystyrene type, polyester, polyamide-based, polyamideimides, poly-aryl compound, polyaryl sulfone class, polyether sulfone, polyphenylene sulfide ethers, polysulfones, polyimide, polyetherimides, tetrafluoroethylene class, the polyethers ketone, polyetheretherketone, polyetherketone ketone, polybenzoxazole class ， polyoxadiazole, polyphenyl and thiazine phenothiazines, the polybenzothiozole class, polypyrazine quinoxaline, polypyromellitimide class, the polyquinoxaline class, polybenzimidazole class, poly-oxindole class, polyoxy isoindoline class, poly-dioxy isoindoline class, poly-triazines, poly-pyridazine class, poly-piperazines, polypyridine class, poly-piperidines, the polytriazoles class, poly-pyrazoles, poly-carborane class, polyoxy bicyclononane class, poly-diphenylene-oxide class, paracoumarone ketone, polyacetals, poly-anhydrides, glymes, EOT class, polyvinyl alcohol, the polyethylene ketone, the polyvinylhalide class, polyethylene nitrile, polyvinyl ester class, the polysulfonate class, the polysulphide class, poly-thioester class, polysulfones, the polysulphonamide class, polyureas, group of polyphosphazenes, polysilazane class, or analogue, perhaps comprise the combination of at least a above-mentioned thermoplastic polymer.Preferred thermoplastic is a polyvinyl alcohol.
Also can use the mixture of thermoplastic polymer.The example of the mixture of thermoplastic polymer comprises acrylonitrile-butadiene-styrene (ABS)/nylon, PC, acrylonitrile-butadiene-styrene (ABS)/polyvinyl chloride, polyphenyl ether/styrene, polyphenyl ether/nylon, polysulfones/acrylonitrile-butadiene-styrene (ABS), polycarbonate/thermoplastic polyurethane, polycarbonate/polyethylene terephthalate, polycarbonate/polybutylene terephthalate, thermoplastic elastomer alloy, nylon/elastomerics, polyester/elastomerics, polyethylene terephthalate/polybutylene terephthalate, acetal/elastomerics, polyvinyl-maleic anhydride/acrylonitrile-butadiene-styrene (ABS), polyether-ether-ketone/polyethersulfone, polyethylene/nylon, polyethylene/polyacetal etc., and the mixture that comprises at least a above-mentioned thermoplastic polymer.
This thermoplastic polymer preferably has the weight-average molecular weight of the 1000-1000000 gram/mole of measuring by gel permeation chromatography (GPC).In one embodiment, the weight-average molecular weight of this thermoplastic polymer is a 3000-500000 gram/mole.In another embodiment, the weight-average molecular weight of this thermoplastic polymer is a 5000-100000 gram/mole.In another embodiment, the weight-average molecular weight of this thermoplastic polymer is a 10000-30000 gram/mole.It should be noted that for this specification sheets, all scopes all comprise end value and capable of being combined.
Preferred thermoplastic is that weight-average molecular weight is the polyvinyl alcohol of 13000-23000 gram/mole.In one embodiment, the degree of hydrolysis of this polyvinyl alcohol is more than or equal to 80 moles of %.In another embodiment, the degree of hydrolysis of this polyvinyl alcohol is more than or equal to 50 moles of %.In another embodiment, the degree of hydrolysis of this polyvinyl alcohol is more than or equal to 20 moles of %.Molecular fraction is based on the total moles of polyvinyl alcohol.
The content of this thermoplastic polymer is 0.001-2wt%.In one embodiment, the content of this thermoplastic polymer is 0.01-1.7wt%.In another embodiment, the content of this thermoplastic polymer is 0.1-1.5wt%.As here and used in this specification, each weight percentage all is based on the gross weight of polishing composition.
Polyvinylpyrrolidone is a 100-1000000 gram/mole by the weight-average molecular weight that GPC measures.In one embodiment, the weight-average molecular weight of this polyvinylpyrrolidone is a 500-500000 gram/mole.In another embodiment, the weight-average molecular weight of this polyvinylpyrrolidone is a 1000-250000 gram/mole.In another embodiment, the weight-average molecular weight of this polyvinylpyrrolidone is a 5000-100000 gram/mole.The typical weight-average molecular weight of polyvinyl pyrrolidone polymers is a 8000-12000 gram/mole, most preferably the nominal weight-average molecular weight of 10000 gram/moles.
In polishing composition, add thermoplastic polymer and polyvinylpyrrolidone when making the polished surface at the semiconductor-based end compare to use the polishing composition that does not have thermoplastic polymer surfaceness reduce, and scratch is less.For this specification sheets, remove the variation that speed refers to time per unit thickness, for example dust/minute.
The content of polyvinylpyrrolidone in polishing composition is generally 0.001-1wt%.In one embodiment, the content of polyvinylpyrrolidone is 0.01-0.85wt%.In another embodiment, the content of polyvinylpyrrolidone is 0.1-0.75wt%.
Wish to use polyvinylpyrrolidone and thermoplastic polymer with 1: 10 to 100: 1 weight ratio respectively.In one embodiment, wish to use polyvinylpyrrolidone and thermoplastic polymer with 1: 5 to 50: 1 weight ratio respectively.In another embodiment, wish to use polyvinylpyrrolidone and thermoplastic polymer with 1: 5 to 60: 1 weight ratio respectively.In another embodiment, wish respectively with 1: 3-10: 1 weight ratio is used polyvinylpyrrolidone and thermoplastic polymer.
This polishing composition preferably includes and is used for the abrasive that " machinery " removes capping layer (cap layer) and blocking layer.The preferred colloidal state abrasive of this abrasive.The example of suitable abrasive comprises: inorganic oxide, and the inorganic oxide with oxyhydroxide coating, metal boride, metallic carbide, metal nitride perhaps comprises the combination of at least a above-mentioned abrasive.Suitable inorganic oxide comprises, for example, and silicon oxide (SiO 2), be coated with the silicon oxide particle of hydrated aluminum oxide, be coated with the various non-axle ellipsoidal particle that waits of silicon oxide, be coated with the alumina particle of cerium oxide hydroxide particles, aluminum oxide (Al 2O 3), titanium oxide (TiO 2), zirconium white (ZrO 2), cerium oxide (CeO 2), manganese oxide (MnO 2) and comprise the combination of at least a above-mentioned inorganic oxide.
It is found that alumina particle can form pure aluminium silicate.Pure aluminium silicate be can with silicon oxide surface bonded amphiprotic substance.Therefore, pure aluminium silicate is in case form, and just trends towards being retained in the surface of silicon oxide and to its protection.Can obtain the aluminum oxide of various ways, as Alpha-alumina, gama-alumina, δ-aluminum oxide and amorphous (amorphous) aluminum oxide.The example of suitable aluminum oxide is boehmite (AlO (OH)).Also can use the improvement form of these inorganic oxides such as the inorganic oxide particles of polymer overmold if desired.Suitable metallic carbide, boride, nitride comprise, for example, and silicon carbide, silicon nitride, carbonitride of silicium (SiCN), norbide, wolfram varbide, zirconium carbide, aluminum boride, tantalum carbide, titanium carbide and comprise at least a above-mentioned metallic carbide, boride, the mixture of nitride.If desired, also can use diamond as abrasive.Alternative abrasive also comprises polymer beads and coated polymeric particles.Preferred abrasive is a colloided silica.
The average particle size particle size of this abrasive is less than or equal to 200 nanometers (nm), to prevent too much metal depression and dielectric erosion.For this specification sheets, particle size refers to the average particle size particle size of abrasive.Wish that the abrasive that uses has the average particle size particle size that is less than or equal to 100 nanometers, preferably is less than or equal to 75 nanometers, and preferably is less than or equal to 50 nanometers.When the average particle size particle size of silicon oxide is the 10-50 nanometer, minimum metal depression and dielectric erosion have advantageously been produced.Most preferably, the average particle size particle size of silicon oxide is the 20-40 nanometer.In addition, preferred abrasive can comprise additive, as dispersion agent so that improve the stability of abrasive.One of this abrasive is the colloided silica that originates from French Clariant S.A of Puteaux.If polishing composition does not contain abrasive, Dian selection at this moment and adjusting become more important for glossing.For example, for the composition of some oxygen-free silicon, fixed grinding pad can improve polishing performance.
Low abrasive concentration can be by reducing the defective that unwanted grinding causes, and scratch for example is to improve the polishing performance of glossing.The abrasive that has relatively little particle size by employing, and, can keep better control to nonferrous metal interconnects and the dielectric removal speed of low-k with low abrasive concentration preparation polishing composition.
The consumption of wishing abrasive is 0.05wt%-40wt%.In one embodiment, the consumption of wishing abrasive is 0.1-10wt%.In another embodiment, the consumption of wishing abrasive is 0.5-5wt%.
Wish to comprise in the polishing composition that oxygenant is to promote the removal of nonferrous metal interconnects, nonferrous metal interconnects such as aluminium, aluminium alloy, copper, copper alloy, gold, au-alloy, nickel, nickelalloy, the platinum metals, platinum-group metal alloy, silver, silver alloys, tungsten and tungstenalloy perhaps contain the combination of above-mentioned at least a metal.Suitable oxygenant comprises, for example, and hydrogen peroxide, single persulphate, iodate is crossed magnesium phthalate, peracetic acid and other peracid, persulphate, bromate, periodate, nitrate, molysite, cerium salt, manganese (Mn) (III), Mn (IV), Mn (VI) salt, silver salt, mantoquita, chromic salts, cobalt salt, halogen, hypochlorite, and comprise the combination of above-mentioned at least a oxygenant.Preferred oxygenant is a hydrogen peroxide.It should be noted that before closing on use oxygenant is added among the polishing composition sometimes, in the case, oxygenant is contained in the isolating packing.In one embodiment, the content of oxygenant is 0.1-10wt%.In another embodiment, the content of oxygenant is 0.2-5wt%.
This polishing composition also preferably comprises corrosion inhibitor, is also referred to as membrane-forming agent usually.Corrosion inhibitor can be that any substrate parts surface that can chemically bind to forms the compound of chemical complex or the mixture of compound, and wherein this chemical complex is not metal oxide or metal hydroxides.This chemical complex can be used as passivation layer and suppresses metal interconnected surface metal-layer dissolving.
Preferred corrosion inhibitor is benzotriazole (BTA).In one embodiment, polishing composition can comprise a large amount of relatively BTA inhibitor to reduce the removal speed of interconnection.The content of inhibitor is up to 10wt%.In one embodiment, the content of inhibitor is 0.025-4wt%.In another embodiment, the content of inhibitor is 0.25-1wt%.When using BTA, can use with the concentration that reaches its solubility limit in polishing composition, this concentration can be up to the saturated limit in 2wt% or the polishing composition.Preferred BTA concentration is 0.0025-2wt%.Selectively, can in polishing composition, add auxiliary corrosion inhibitor.Auxiliary corrosion inhibitor be tensio-active agent as, for example, anion surfactant, nonionogenic tenside, amphoterics and polymkeric substance, perhaps organic compound such as azole (azoles).In addition, azole can be used for fixing the removal speed of (toggle) or control copper.For example, this auxiliary inhibitor can comprise imidazoles, and tolyl-triazole or their mixture combine with BTA's.The interpolation of tolyl-triazole can reduce the removal speed of copper, and the interpolation of imidazoles can increase the removal speed of copper.The combination of tolyl-triazole and imidazoles can be used for removal speed fixing or control copper.
This polishing composition has alkaline pH with metal interconnected removal speed and low-k or ultralow-k dielectric medium rate fixing or the control expectation.Usually wish that this polishing composition has at least 7 pH.In one embodiment, the pH value of polishing composition can be more than or equal to 8.Polishing composition also comprises inorganic or organic pH regulator agent changing the pH value of polishing composition, and proper acidic pH value conditioning agent comprises, for example, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid etc., and comprise the combination of above-mentioned at least a acid ph value conditioning agent.Preferred pH value conditioning agent is a nitric acid.Also can in polishing composition, use alkaline pH value conditioning agent.The example of suitable pH value conditioning agent has sodium hydroxide, ammonium hydroxide, potassium hydroxide etc., and the combination that comprises above-mentioned at least a alkaline pH value conditioning agent.The surplus of this waterborne compositions is a water, and is preferably deionized water.
Selectively, polishing composition can comprise chelating or coordination agent and adjusts copper and remove speed to remove speed with respect to barrier metal.This chelating or coordination agent are by forming the removal speed that the chelated mineral title complex improves copper with copper.The typical coordination agent that selectively is used for polishing fluids comprises acetate, citric acid, methyl aceto acetate, oxyacetic acid, lactic acid, oxysuccinic acid, oxalic acid, Whitfield's ointment, Thiocarb, succsinic acid, tartrate, Thiovanic acid, glycine, L-Ala, aspartic acid, second diamino, trimethylene diamines, propanedioic acid, pentanedioic acid, 3-hydroxybutyric acid, propionic acid, phthalic acid, m-phthalic acid, 3-hydroxyl Whitfield's ointment, 3,5-dihydroxyl Whitfield's ointment, gallate, glyconic acid, pyrocatechol, pyrogallol, gallate, tannic acid and their salt.Preferably, the coordination agent that uses in polishing fluids is a citric acid.Most preferably, polishing fluids comprises coordination and/or the sequestrant that is up to 15wt%.
Selectively, this polishing composition also can comprise buffer reagent such as various organic and mineral acid, reaches amino acid or their pKa values and is equal to or greater than 5 salt.Selectively, this polishing composition also can comprise defoamer, and as nonionogenic tenside, it comprises ester, ethylene oxide, alcohol, ethoxy compound, silicon compound, fluorine cpd, ether, glycosides and their derivative, and comprise above-mentioned at least a surfactant mixtures.Defoamer can also be an amphoterics.Polishing composition also comprises pH buffer reagent, sterilant and defoamer alternatively.
Usually preferably on the semiconductor-based end, use this polishing composition with non-iron interconnection.The metal that is applicable to interconnection comprises, for example, aluminium, aluminium alloy, copper, copper alloy, gold, au-alloy, nickel, nickelalloy, the platinum metals, platinum metal alloy, silver, silver alloys, tungsten and tungstenalloy perhaps comprise the combination of above-mentioned at least a metal.Preferred interconnecting metal is a copper.
Polishing composition can make polissoir operate under the low pressure less than 21.7kPa (3psi).Preferred pad pressure is 3.5-21.7kPa (0.5-3psi).In this scope, the preferred pressure that is less than or equal to 13.8kPa (2psi) that uses is more preferably less than or equals 10.3kPa (1.5psi), and most preferably is less than or equal to the pressure of 6.9kPa (1psi).Most preferably, polishing adopt hereinafter shown in polishing pad and the condition of embodiment under.Low polishing pad pressure improves polishing performance by reducing scratch with other undesirable polishing defect, and reduces the damage to hard brittle material.For example, when being exposed to when heavily stressed, advanced low-k materials can break and layering.The polishing composition that comprises thermoplastic polymer and polyvinylpyrrolidone advantageously provides high blocking layer and capping layer is removed speed, is convenient to control nonferrous metal interconnects simultaneously and is derived from for example low-k of the organic materials of carbon doped oxide and the removal speed of ultralow-k dielectric layer.In an example embodiment, can adjust or regulate polishing composition and do not damage low-k and ultralow-k dielectric layer basically so that obtain high barrier removal rates.Can in having the patterned wafers of multiple live width, advantageously use this polishing composition to reduce corrosion.
Use porous polyurethane polishing pad, record under the pad pressure perpendicular to the 3.5-21.7kPa of integrated circuit (IC) wafer, the tantalum nitride of this polishing composition is removed speed ratio copper and is removed the big 2-4 of speed doubly.Use porous polyurethane polishing pad, record under the pad pressure perpendicular to the 3.5-21.7kPa of integrated circuit (IC) wafer, the tantalum nitride of this polishing composition is removed speed and is removed speed more than or equal to 2 times low-K dielectric.Adopt the condition among the embodiment, special being applicable to determines that optionally polishing pad is IC1010 TMPorous is filled the polyurethane polishing pad.Polishing composition can produce before polishing operation or in its process.If produce in during polishing operation, polishing fluids can be introduced the polishing interface, at this moment can part or all of particle be introduced the polishing interface by mode from the polishing pad release particles.
To describe some embodiments of the present invention in detail with the following example below
Embodiment
The term of used material is as shown in table 1 below in the polishing composition of the following example.Klebosol1501-50 is a kind of silicon oxide available from Clariant, has the pH that the 30wt% median size equals the silicon oxide particle of 50 nanometers and has 10.5-11.By use deionized water with this diluted sample to the 12wt% silicon oxide particle.
Table 1
Term Title
BTA Benzotriazole
CA Citric acid
Klebosol 1501-50 Colloided silica
H 2O 2 Hydrogen peroxide
Polyvinylpyrrolidone Available from ISP technology, has the molal weight of 10000 gram/moles
Polyvinyl alcohol Available from Aldrich, have the molal weight of 13000-23000 gram/mole, degree of hydrolysis is 87-89 mole %.
The polishing composition that present embodiment is used to confirm to contain polyvinylpyrrolidone and polyvinyl alcohol can be used to change the removal speed of copper effectively, reduces low-k and the dielectric removal speed of ultralow-k as carbon doped oxide simultaneously.The Mirra type wafer polishing machine that the polishing test utilizes Applied Materials to provide.Polishing pad is the IC1010 that Rohm and Haas Electronic Material CMP Technologies provides TMBefore each run, this pad is adjusted.With the pressure of 13.78kPa (2psi), the carriage rotating speed of 120 rev/mins of (rpm) table speed and 114rpm carries out this polishing process.Polishing composition fill rat (slurry flow) is 200 ml/min (ml/min).The blank wafer of 200mm is all adopted in all tests.
In this embodiment, it is as shown in table 2 to use different polyvinylpyrrolidones and polyvinyl alcohol concentration to prepare several polishing compositions.The optional additive of prescription is the ammonium chloride of 0.01wt% and the sterilant of 0.005wt% (activeconstituents) shown in the adding table 2, as KORDEK (available from Rohmand Haas Company).Simultaneously the contrast polishing composition that only contains polyvinylpyrrolidone is tested.Contrast polishing composition shown in the table 2 is sample 1,5 and 6.Table 2 has shown the removal speed (RR) with tantalum nitride (TaN), copper (Cu), TEOS, carbon doped oxide (CDO) and the SiCN of dust/minute expression.CDO is available from NovellusSystems, the CORAL low K dielectrics of Inc.
Table 2
Sample # ????CA ??(wt％) ??BTA ??(wt％) ??PVP ??(wt％) ??PVA ??(wt％) PVP/PVA Wt ratio ????TEOS ????RR ????Cu ????RR ????TaN ????RR ????CDO ????RR ???SiCN ????RR Cu/TaN RR ratio
????1* ????0.30 ????0.05 ????0.60 ????- ????421 ????235 ????ND ????41 ????187 ????-
????2 ????0.30 ????0.05 ????0.60 ????0.10 ????6 ????373 ????159 ????606 ????140 ????283 ????0.26
????3 ????0.30 ????0.05 ????0.60 ????1.00 ????0.6 ????263 ????47 ????645 ????121 ????227 ????0.07
????4 ????0.30 ????0.05 ????0.60 ????0.50 ????1.2 ????299 ????83 ????607 ????150 ????254 ????0.13
????5* ????0.30 ????0.05 ????0.60 ????- ????441 ????232 ????705 ????69 ????239 ????0.32
????6* ????0.30 ????0.05 ????0.20 ????- ????648 ????123 ????903 ????155 ????ND ????0.13
????7 ????0.30 ????0.05 ????0.20 ????0.10 ????2 ????623 ????80 ????ND ????260 ????438 ????-
????8 ????0.30 ????0.05 ????0.3 ????0.005 ????60 ????444 ????357 ????637 ????365 ????512 ????0.56
????9 ????0.30 ????0.05 ????0.3 ????0.05 ????6 ????581 ????173 ????696 ????273 ????478 ????0.24
RR=is with the removal speed of dust/minute expression
* comparative examples
The ND=undetermined
As can be seen from Table 2, with the increase of polyvinyl alcohol to the polyvinylpyrrolidone ratio, the removal speed of copper reduces, and the removal speed of low-k dielectric medium or carbon doped oxide such as CDO layer still remains on low-down speed.Also can find out, preferably in the removal speed that keeps low-k is changed in dielectric removal rate-controlling copper.Can find out also that from table 2 polishing composition that has not only contained polyvinyl alcohol but also contained polyvinylpyrrolidone also can be used for keeping the removal speed of the raising of blocking material such as TEOS and tantalum nitride (TaN).

Claims (10)

1. be applicable to the polishing composition of polishing semiconductor substrate, said composition comprises:
The thermoplastic polymer of 0.001-2wt%; With
The polyvinylpyrrolidone of 0.001-1wt%; Wherein change the removal speed of the weight ratio control nonferrous metal interconnects of the relative polyvinylpyrrolidone of thermoplastic polymer.
2. composition as claimed in claim 1, wherein this thermoplastic polymer is a polyacetals, polyacrylic, polycarbonate-based, polystyrene type, polyester, polyamide-based, polyamideimides, poly-aryl compound, the polyaryl sulfone class, polyether sulfone, polyphenylene sulfide ethers, polysulfones, polyimide, polyetherimides, the tetrafluoroethylene class, polyethers ketone, polyetheretherketone, the polyetherketone ketone, polybenzoxazole class, polyoxadiazole class, polyphenyl and thiazine phenothiazines, polybenzothiozole class, polypyrazine quinoxaline, the polypyromellitimide class, polyquinoxaline class, polybenzimidazole class, poly-oxindole class, polyoxy isoindoline class, poly-dioxy isoindoline class, poly-triazines, poly-pyridazine class, poly-piperazines, the polypyridine class, poly-piperidines, polytriazoles class, poly-pyrazoles, poly-carborane class, polyoxy bicyclononane class, poly-diphenylene-oxide class, paracoumarone ketone, polyacetals, poly-anhydrides, glymes, EOT class, polyvinyl alcohol, the polyethylene ketone, polyvinylhalide class, polyethylene nitrile, the polyvinyl ester class, the polysulfonate class, polysulphide class, poly-thioester class, polysulfones, the polysulphonamide class, polyureas, poly-phosphorus eyeball class, the polysilazane class perhaps comprises the combination of at least a above-mentioned thermoplastic polymer.
3. composition as claimed in claim 1, said composition further comprises the silicon oxide particle of 0.1-40wt%.
4. composition as claimed in claim 1, wherein this thermoplastic polymer is that weight-average molecular weight is the polyvinyl alcohol that 1000-1000000 gram/mole and degree of hydrolysis are at least 20 moles of %, wherein this molecular fraction is based on the total mole number of polyvinyl alcohol.
5. composition as claimed in claim 1, wherein the weight-average molecular weight of this polyvinylpyrrolidone is a 100-1000000 gram/mole.
6. composition as claimed in claim 1, wherein the weight ratio of polyvinylpyrrolidone that exists in the polishing composition and thermoplastic polymer is respectively 1: 10-100: 1.
7. be applicable to the polishing composition of polishing semiconductor substrate, said composition comprises:
The 0.001-2wt% weight-average molecular weight is the polyvinyl alcohol of 13000-23000g/ mole;
The 0.001-1wt% weight-average molecular weight is the polyvinylpyrrolidone of 3000-10000g/ mole;
Be up to the corrosion inhibitor of 10wt%;
Be up to the coordination agent of 15wt%;
Be up to the oxygenant of 10wt%; With
The silica abrasive of 0.1-40wt%; Wherein the pH value of this polishing composition is at least 7, and wherein changes the removal speed of the controlled manufacture-illegal iron interconnection of weight ratio of thermoplastic polymer and polyvinylpyrrolidone.
8. the method for polishing semiconductor substrate, this method comprises the steps:
The thermoplastic polymer that will comprise 0.001-2wt%; Be applied to the semiconductor-based end with the polishing composition of the polyvinylpyrrolidone of 0.001-1wt%; With
Be less than or equal to polishing semiconductor substrate under 21.7 kPas the pad pressure, the weight ratio that wherein changes thermoplastic polymer and polyvinylpyrrolidone is controlled the removal speed of non-iron interconnection.
9. method as claimed in claim 8, wherein this polishing composition provide easily be less than or equal to 150 dusts/minute the low-K dielectric layer remove speed.
10. method as claimed in claim 8, wherein this polishing composition provide easily more than or equal to 150 dusts/minute the low-K dielectric layer remove speed.
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